Activation of Hydrogen Peroxide by Diphenyl Diselenide for Highly Enantioselective Oxaziridinium Salt Mediated Catalytic Asymmetric Epoxidation

Benjamin R. Buckley; Claire E. Elliott; Yohan Chan; Nicholas Dreyfus; Philip C. Bulman Page

doi:10.1055/s-0033-1339681

Synlett, Table of Contents

Synlett 2013; 24(17): 2266-2270
DOI: 10.1055/s-0033-1339681

letter

Activation of Hydrogen Peroxide by Diphenyl Diselenide for Highly Enantioselective Oxaziridinium Salt Mediated Catalytic Asymmetric Epoxidation

Benjamin R. Buckley*

^aDepartment of Chemistry, Loughborough University, Ashby Road, Loughborough, Leicestershire, LE11 3TU, UK Fax: +44(1509)223925 Email: b.r.buckley@lboro.ac.uk

,

Claire E. Elliott

^aDepartment of Chemistry, Loughborough University, Ashby Road, Loughborough, Leicestershire, LE11 3TU, UK Fax: +44(1509)223925 Email: b.r.buckley@lboro.ac.uk

,

Yohan Chan

^bSchool of Chemistry, University of East Anglia, Norwich, Norfolk NR4 7TJ, UK Email: p.page@uea.ac.uk

,

Nicholas Dreyfus

^cEli Lilly, Erl Wood Manor, Erl Wood, Windlesham, Surrey, UK

,

Philip C. Bulman Page*

^bSchool of Chemistry, University of East Anglia, Norwich, Norfolk NR4 7TJ, UK Email: p.page@uea.ac.uk

› Author Affiliations

Abstract

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Abstract

The first reported use of benzeneperseleninic acid as a catalytic mediator for oxaziridinium ion catalysed epoxidation is described, providing reaction rates and ee values (up to 85%) similar to those reported when using oxone as the stoichiometric oxidant. A dual catalytic cycle is proposed, in which diphenyl diselenide is initially converted into the perseleninic acid, which in turn oxidises an iminium ion to the corresponding oxaziridinium species, thus facilitating asymmetric oxygen transfer to an alkene.

Key words

epoxidation - iminium salt - oxaziridinium - diphenyl diselenide - oxidation

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References

References and Notes

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15 2,2′-Bis(bromomethyl)octahydrobinaphthalene was prepared according to the method of Ruan (see ref. 21). The dibromide (0.20 g, 0.45 mmol) and (S,S)-acetonamine (0.20 g, 0.45 mmol) were dissolved in MeCN (30 mL), and K₂CO₃ (0.185 g, 1.34 mmol) was added. The solution was stirred with heating under reflux for 4 h. After cooling to r.t., the solvent was removed under reduced pressure. The residue was dissolved in CH₂Cl₂ (30 mL), washed with H₂O (2 × 30 mL), dried (MgSO₄), filtered and solvents were removed under reduced pressure to afford 7 as a colourless solid (0.20 g, 91%); mp 170–171 ºC; [α]_D ²⁰ –8.4 (c = 0.9, CH₂Cl₂). IR (film): 3052, 2932, 1633, 1599, 1449, 1443, 1388, 1300, 1200, 1142, 1109, 950, 850, 731 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.59 (s, 3 H), 1.64 (s, 3 H), 1.74–1.78 (m, 8 H), 2.12–2.19 (m, 2 H), 2.62–2.65 (m, 3 H), 2.85 (t, J = 6.8 Hz, 4 H), 3.10 (d, J = 12.4 Hz, 2 H), 3.50 (d, J = 12.0 Hz, 2 H), 4.11–4.23 (m, 3 H), 6.90 (d, J = 7.2 Hz, 2 H), 6.99 (d, J = 7.2 Hz, 2 H), 7.26–7.32 (m, 5 H). ¹³C NMR (100 MHz, CDCl₃): δ = 19.2, 22.7, 22.8, 23.0, 23.1, 27.6, 27.7, 29.5, 29.6, 52.8, 59.9, 61.3, 125.9, 126.7, 127.6, 128.0, 132.3, 133.5, 154.9, 137.8, 158.1, 138.7. HRMS (ESI): m/z [M + H⁺] calcd for C₃₄H₄₀NO₂: 494.3059; found: 494.3043. Anal. Calcd for C₃₄H₃₉NO₂: C, 82.72; H, 7.96; N, 2.84. Found: C, 82.52; H, 7.66; N, 2.92. Compound 7 (0.08 g, 0.16 mmol) was dissolved in CH₂Cl₂ (20 mL) and N-bromosuccinimide (0.04 g, 0.19 mmol, 1.2 equiv) was added. The solution was heated under reflux for 4 h. After cooling to r.t., the solvent was removed under reduced pressure. The residue was dissolved in EtOH, and sodium tetraphenylborate (0.06 g, 0.018 mmol, 1.1 equiv), dissolved in the minimum amount of MeCN, was added in one portion, and the reaction mixture was stirred for 5 min. The solvents were removed under reduced pressure to give a yellow residue that was recrystallised from hot EtOH to give 5 as a yellow crystalline solid, washed with cold EtOH and Et₂O (0.10 g, 76%); mp 130–135 °C; [α]_D ²⁰ –10.0 (c = 0.8, CH₂Cl₂). IR (film): 3053, 2936, 1619, 1575, 1488, 1427, 1382, 1202, 1111, 838, 733, 703 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.55–1.62 (d, 6 H), 1.76–2.27 (m, 12 H), 2.53–2.99 (m, 6 H), 3.45–3.71 (m, 3 H), 5.00–5.05 (m, 1 H), 6.73–6.78 (m, 4 H), 6.84–7.11 (m, 10 H), 7.20–7.28 (m, 8 H), 7.29–7.36 (m, 8 H). ¹³C NMR (100 MHz, CDCl₃; mixture of rotamers): δ = 14.2, 18.8, 18.9, 21.0, 21.8, 22.1, 22.2, 22.5, 22.8, 22.9, 23.3, 26.8, 27.8, 27.95, 28.02, 29.5, 29.6, 29.7, 29.6, 29.7, 30.2, 30.6, 30.9, 48.4, 54.8, 55.2, 60.4, 60.5, 63.2, 66.4, 71.7, 73.8, 99.1, 100.4, 122.3, 124.1, 124.7, 124.8, 125.1, 125.4, 125.8, 125.8, 125.9, 127.1, 128.0, 128.2, 128.4, 128.6, 128.8, 128.9, 129.0, 129.7, 130.5, 131.7, 133.8, 134.1, 134.6, 134.9, 135.2, 135.6, 135.8, 136.0, 136.1, 137.7, 138.8, 139.8, 140.4, 140.5, 144.0, 144.6, 146.3, 187.0. HRMS (EI): m/z [M⁺] calcd for iminium cation C₃₄H₃₈NO₂: 492.2895; found: 492.2897. Anal. Calcd for C₅₈H₅₈BNO₂: C, 85.80; H, 7.20; N, 1.73. Found: C, 85.45; H, 6.82; N, 1.63.
16 General Procedure for Epoxidation using Diphenyl Diselenide, Hydrogen Peroxide and Iminium Salt or Amine: The alkene (1.0 equiv) was dissolved in MeCN (2 mL per mmol alkene), and the iminium salt (or amine) catalyst (5 mol%) was added along with diphenyl diselenide (1 mol%). The reaction vessel was cooled in an ice bath for 5 min, and hydrogen peroxide (50%, 3.0 equiv) was added dropwise over 5 min. The reaction progress was followed using TLC, and, when the reaction was complete, Et₂O (20 mL) was added. The mixture was washed twice with H₂O (2 ×) and once with sat. brine, and dried over MgSO₄. The solvents were removed under reduced pressure, and the crude product was purified using column chromatography on silica gel (EtOAc–petroleum ether–Et₃N).
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